Details

Autor(en) / Beteiligte

• Tzeng, Biing‐Chiau
• Chiu, Hsiu‐Hui
• Chang, Jia‐Hen
• Lee, Gene‐Hsiang

Titel

Supramolecular gold(I) compounds with trithiocyanuric acid: Self‐assembly and luminescent properties

Ist Teil von

• Journal of the Chinese Chemical Society (Taipei), 2019-09, Vol.66 (9), p.1064-1071

Ort / Verlag

Weinheim: Wiley‐VCH Verlag GmbH & Co. KGaA

Erscheinungsjahr

2019

Link zum Volltext

Quelle

Wiley Online Library Journals Frontfile Complete

Beschreibungen/Notizen

• [(N3S3)Au(AuPMe3)2]2 (1) and [(N3S3)Au(AuPEt3)2]2 (2) were prepared by treating AuCl(PMe3) or AuCl(PEt3) with H3N3S3 upon deprotonation by trimethylamine to give respective Au6 supermolecules. Using dppm(AuCl)2 instead of AuCl(PMe3) or AuCl(PEt3) to react with H3N3S3 in a similar reaction condition led to a rare heptanuclear supermolecule of [(N3S3)2Au7(dppm)4]Cl (3). It is noted that besides short intramolecular gold(I)⋯gold(I) distances, both compounds 1 and 2 also show intermolecular gold(I)⋯gold(I) distances of 3.067(1) and 3.241(1) Å, resulting in two‐dimensional and one‐dimensional polymeric gold(I) solid, respectively. In fact, compound 1 shows a similar two‐dimensional polymeric gold(I) solid to that of the reported [(N3S3)Au(AuPPhMe2)2]2 with an intermolecular gold(I)⋯gold(I) distance of 3.130(2) Å. Significantly, these intermolecular gold(I)⋯gold(I) distances are well correlated with their cone angles and emission energies. For example, intermolecular gold(I)⋯gold(I) distances increase in the order of 3.067(1) Å < 3.130(2) Å < 3.241(1) Å for PMe3 (118°), PPhMe2 (122°), and PEt3 (132°), and their emission energies also increase in the order of 542 nm < 530 nm < 504 nm, respectively. This work highlights a very good correlation between intermolecular aurophilic interactions and emission energies for a series of Au6 supermolecules, where the cone angle plays a vital role in the self‐assembly process as well. Finally, the emissions for 1–3 are tentatively assigned to the S → Au charge‐transfer transition, whereas they are most probably modified by gold(I)⋯gold(I) interactions. [(N3S3)2Au7(dppm)4]Cl is a rare heptanuclear gold(I) supermolecule. One important feature is that the N3S3(dppmAu2) moiety forms a 10‐mmbered ring with (dppmAu2)S2 instead of a more common 8‐membered ring of (dppmAu2)NS,22 and additionally there is a long intramolecular gold(I)⋯gold(I) distance of 3.725(5) Å.